Treated vinyl and polyester and methods and compositions for the production and use thereof



United States Patent 3,479,198 TREATED VINYL AND POLYESTER AND METH- ODSAND COMPOSITIONS FOR THE PRODUC- TION AND USE THEREOF Julius O. Barth,Aurora, [1]., assignor to The Permalux Company, Aurora, Ill., acorporation of Illinois No Drawing. Continuation-impart of applicationSer. No. 395,331, Sept. 9, 1964, and Ser. No. 447,075, Apr. 9, 1965.This application Sept. 14, 1967, Ser. No.

Int. (:1. B44d 1/12; (309a 3/48 US. Cl. 117-15 12 Claims ABSTRACT OF THEDISCLOSURE This application is a continuation-in-part of applicantscopending applications Ser. No. 395,331, filed Sept. 9, 1964, nowabandoned, and Ser. No. 447,075, filed Apr. 9, 1965, now abandoned.

The instant invention is directed to printed vinyl and polyester and tomethods and novel compositions adapted to be utilized for printing ontothe vinyl and polyester surfaces. The invention is particularly directedto systems providing for the treatment of vinyl and polyester surfaceswhereby printing inks and similar materials can be efficiently appliedto said surfaces.

The use of vinyl and polyester materials is Well known, and theapplication of printing inks and similar materials onto such surfaceshas become increasingly popular. Printing applications usually involvethe display of written material or decorative designs on the surfaces.

Vinyl and polyester materials are employed to a large extent in theproduction of labels or other items where the materials are in sheetform. Containers or other three-dimensional objects are also formed ofsuch materials and even though the invention will be described relativeto vinyl and polyester materials in sheet form, it will be understoodthat the invention is directed to all items which have exposed vinyl orpolyester surfaces.

In the production of labels or the like, sheets or rolls of material maybe provided with adhesive on one surface whereby the sheets can bereadily secured in place. The opposite surface of the sheets carriesprinted lettering or designs employed for informational and decorativepurposes. Where a pressure sensitive adhesive or the like is appliedduring production, a protective sheet of paper is located over theadhesive side of the vinyl sheet, and this paper can be readily peeledoff before application. Otherwise, adhesive or other securing means canbe provided as desired.

As noted in the aforementioned copending applications, printing ontovinyl or polyester surfaces, whether oriented or non-oriented, presentscertain problems. The difficulties experienced arise primarily due tothe fact that inks other than vinyl and acrylic base inks will notadhere to vinyl, and all types of ink have insufficient or no adhesionwith respect to polyester surfaces. This difficulty can apparently beexplained by the fact that in the case of vinyl surfaces, inks otherthan vinyl and acrylic base inks are chemically unrelated with thesurfaces. In the silk screen and graphic arts, generally the approach'ice to ink adhesion is to develop special ink formulae to achieveadhesion to the substrate being printed. Kuhn Patent No. 2,686,736 andGoldstein Patent No. 2,872,423 illustrate this approach.

Vinyl and acrylic base inks will provide satisfactory adherence whenapplied to vinyl, but this does not apply to a polyester surface;however, it has been found that the chemical compositions of such inksmust be maintained within relatively narrow limits, with these limitsdepending upon the particular type of surface involved. Productionproblems and inconsistent quality frequently result when such inks areemployed.

Vinyl and acrylic base inks are also undesirable in many instances sincethese inks are characterized by low gloss, poor colors, and lack offullness and depth. Since printed products are in many cases employedfor advertising purposes, the character of the printed surfaces wherevinyl and acrylic base inks are employed is considered undesirable.

It is also recognized that under current production methods andtechniques, an extremely limited amount of colored vinyl film can beproduced. Coloring of vinyl is accomplished by the addition of pigmentsor dyes to the vinyl plastic mass when it is in a molten or semi-moltenstate. The viscosity of this mass when it is in this semifluid state isextremely high. This makes uniform dispersion of pigments extremelydifficult, if not impossible. Since the film is extruded intothicknesses ranging from one mil upwards, the uneven pigment dispersionresults in streaks and uneven coloring and hiding. Furthermore, manypigments become reactive in the presence of even slightly elevatedtemperatures. For these reasons, the production of commerciallyacceptable colored vinyl film by current technologies is costly andimpractical. Furthermore, the addition of pigments to the plastic massresults in a film of considerably reduced tensile strength.

From the commercial standpoint, there is considerable demand for a largevariety of colored vinyl film but even if current techniques permitted,it would be economically impractical to build inventories of largevarieties of colored film in anticipation of customer requirements.

The aforementioned copending applications are generally directed tosystems-involving the treatment of surfaces whereby inks and similarmaterials which vary widely in chemical composition can be applied tothe surfaces. In particular, the prior applications disclosecompositions which are adapted to be applied over vinyl and polyestersurfaces as films whereby printing operations involving the applicationof ink on to the films can be undertaken. The compositions disclosedprovide for excellent adhesion of the printing inks with respect tovinyl and polyester substrates. A wide variety of inks can be employedwhere the disclosed composition is first applied over the-vinyl orpolyester surfaces, and for that reason, vinyl, and also polyestermaterials can be utilized in a wide variety of applications whichrequire special types of printing material.

Procedures described in the prior applications have been found to becompletely satisfactory where coating materials of the specifiedcompositions are applied'over vinyl and polyester surfaces. The printingapplied over the vinyl surfaces having the intercoat compositionsthereon will adhere to a highly satisfactory degree and the normalcharacteristics of the printing ink, such as gloss, can be readilyachieved. Furthermore, it has been found that the printed sheets displayremarkable stain resistance.

As explained in Ser. No. 447,075, it is sometimes necessary to vary theintercoat compositions in order to increase production rates and toaccommodate available drying facilities. Specifically, air drying willslow down operations and where forced drying is resorted to,

some compositions present difficulties. It was also found that the useof acrylic or alkyd-acrylic copolymers in combination with a vinylchloride-acetate copolymer greatly enhanced the compositions, and thatcertain solvent combinations also provided highly desirable results.

It is an object of this invention to provide improvements in vinyl andpolyester materials through the use of intercoat compositions andmethods whereby coating materials such as printing inks can be appliedover vinyl and polyester surfaces to achieve ideal adherence and notablyimproved durability.

It is a more particular object of this invention to provide compositionsof the type described which are characterized by excellent stabilityeven when baked immediately after application whereby highly efficientoperations can be undertaken.

It is a further object of this invention to provide vinyl and polyesterfilm having the appearance of colored film whereby printing operationscan be conducted on films having a variety of backgrounds.

These and other objects of this invention will appear hereinafter and itwill be understood that the specific examples hereinafter set forth areprovided solely for purposes of illustration and not by way oflimitation.

The intercoat composition of this invention generally comprises amixture of various chemicals which form a composition uniquely suitablefor application over vinyl and polyester surfaces. As set forth in Ser.No. 395,331, the composition must include as essential ingredients avinyl chloride-acetate copolymer in combination with a solvent. In Ser.No. 447,075, reference is made to the addition of at least one acrylicpolymer or alkyd-acrylic copolymer, and a combination of ketones as thesolvents. This application also referred to the inclusion of at leastone modified formaldehyde resin or epoxy resin, at least one suitablestabilizer or stabilizer system, and at least one aromatic hydrocarbon.

The compositions described in Ser. No. 395,331 consist essentially of avinyl chloride-acetate copolymer or modified vinyl chloride-acetatecopolymer in combination with a solvent selected from the groupconsisting of ketones, nitro compounds, esters, chlorinated hydrocarbonsand aromatic hydrocarbons. The film when applied preferably includesfrom to percent by weight of the vinyl chloride-acetate copolymer andthe balance solvent, although up to percent by weight of the copolymermay be employed, it being understood that the solvent evaporates and,therefore, the initial solvent proportion is important primarily due toapplication convenience.

The addition of at least one acrylic polymer or alkydacrylic copolymerin amounts between 7.5 and 20 percent by weight as set forth in Ser. No.447,075 greatly contributes to the durability and permanent flexibilitywhich is achieved in the intercoat films of the invention. It has beenfound that the presence of such materials in the applied film virtuallyeliminates any adhesion problem even when baking is utilized to speed upthe drying operation and to thereby provide improvements in productionefficiency.

Another addition contemplated comprises up to one percent by weightpolyvinyl chloride. This ingredient can be tolerated in such minorproportions (up to about five percent by weight of the final film) andcertain improvements in durability and toughness will be provided.

The use of a formaldehyde resin or an epoxy resin is preferred since ithas been found that a crosslinking effect is achieved by the addition ofsuch compounds. Without the thermosetting resins, the intercoat may beair-dried or force-dried, but baking is necessary to convert thethermosetting combination. In some cases, we obtain a physicaldispersion of the crosslinking resin through the film structure. Inother cases, there is a chemical reaction or condensation of the freehydroxyl groups in the vinyl chlorideaeetate copolymer and thecross-linking resin.

The principal reasons for adding the thermosetting resin are to increasethe solvent-resistance of the coating, to improve the surface hardnessand gloss, to improve the print-resistance, to improve the adhesion, andto minimize the softening at higher temperatures.

The stabilizers or stabilizer systems employed preferably comprisestabilizers which provide heat resistance plus resistance toultra-violet light. Available stabilizers provide distinct improvementsin the intercoat composition after a baking operation, and otherstabilizers also provide improvements in the life of the vinyl orpolyester product by reason of their resistance to ultra-violet light.The stabilizer systems which are preferred comprise a combination ofsuch stabilizers.

Aromatic hydrocarbons such as toluol, and xylol are employed since suchmaterials are relatively inexpensive, and these materials provide anideal diluent for the intercoat composition. It will be appreciated thatacrylics and other compounds may be supplied in these hydrocarbons,thereby providing at least a portion of the diluent is employed in orderto maintain the intercoat composition in a state such that thecomposition can be readily applied over the surfaces. Exuellent flowcharacteristics in the final product are achieved when such diluents areadded in amounts such that the total solids content of the compositionwill not exceed 20 percent by weight. This ratio of solid to liquidrepresents a preferred feature of the invention although any solidcontent and solvent combination which provides suitable fiowcharacteristics is contemplated.

The intercoat of film can be applied by any conventional method such asspraying, roller coating, silk screen printing, brushing with a doctorblade or by any other suitable method for coating application.Individual sheets could be coated, however, it is most advantageous toprovide film in continuous rolls and to then roll up the coated film,particularly where the film is to be transported to a different locationfor printing.

For use as the vinyl chloride-acetate copolymer, and modified vinylchloride-acetate copolymer, it is contemplated that a variety offormulations will be satisfactory. Typical copolymers contain aboutpercent by weight vinyl chloride and 10 percent by Weight vinyl acetatewith modified copolymers including additives such as vinyl alcohol andmaleic acid. Specifically, Bakelite (Union Carbide) designations VMCC,VAGH, VMCH, VAGD, VYLF, VYHH, VYNS, and VYNW are highly satisfactory.

The compositions of these copolymers are as follows:

VAGH-A partially hydrolyzed vinyl chloride-vinyl acetate copolymerhaving a vinyl chloride content of 91%. (Described in Bakelite VinylResin Product Data Booklet J-2198-C/116-4.)

VYHHA vinyl chloride-vinyl acetate copolymer having a composition ofapproximately 87% vinyl chloride; 13% vinyl acetate. (Described inBakelite Vinyl Plastics Product Data Booklet J-2195-B/026-4.)

VMCC-A modified vinyl chloride-vinyl acetate copolymer having acomposition of approximately 84% vinyl chloride; 15% vinyl acetate; and0.8% interpolymerized maleic acid. (Described in Bakelite Vinyl ResinProduct Data Booklet J2453A/0965.)

VMCH-A modified vinyl chloride-vinyl acetate copolyrner' having acomposition of about 86% vinyl chloride; 13% vinyl acetate; and 1%interpolymerized dibasic acid (0.7-0.8 carboxyl). (Schildknecht entitledVinyl and Related Polymers published by Wiley, 1952.

VYLF-A vinyl chloride-vinyl acetate copolymer having a composition ofapproximately 87% vinyl chloride; and 13% vinyl acetate.

VAGD-A vinyl chloride-vinyl acetate copolymer having a vinyl chloridecontent of 91%; a vinyl acetate con tent of 3% and approximately 5.9%vinyl alcohol.

VYNS-A vinyl chloride-vinyl acetate resin containing approximately 90%vinyl chloride and vinyl acetate having an inherent viscosity of 0.80measured on .2 g. in cyclohexanone at 25 C.

VYNW-A vinyl chloride-vinyl acetate copolymer containing approximately97% vinyl chloride; 3% vinyl acetate having an inherent viscosity of1.07 measured at .2 g. in cyclohexanone at 25 C.

The following comprises a table listing several suitable solvents;however, it wil be appreciated that the list is not exclusive:

In the aforementioned applications, isophorone has been referred to as adesirable solvent. It has now been found that cyclohexanone is equallyas effective and is in certain respects superior to isophorone and,accordingly, cyclohexanone represents a preferred substitute forisophorone. Similarly, ethylacetate is a highly suitable substitute formethylethyl ketone, heretofore considered to be a preferred ingredient.

The following illustrates the composition ranges for an intercoatcomposition where the vinyl chloride-acetate copolymer is used withoutalkyd or alkyd-acrylic:

TABLE I Ingredients: Percent by Weight I Vinyl chloride-acetatecopolymer 10-20 Ketones 80-90 A composition of this type is preferablyprepared by mixing the ketones at room temperature and adding thecopolymer to this mixture.

The following tables illustrate the ranges for the various elementswhere the acrylic or alkyd-acrylic polymers are employed:

TABLE 11 Ingredients: Percent by weight Vinyl chloride acetate copolymer3.0-12.0

Acrylic polymers and/or alkyd-acrylic copolymer 7.5-20.0

Ethylacetate, methylethyl-ketone and/or methylisobutyl ketone 45.0-75.0Cyclohexanone or isophorone 1.0-5.0

Modified formaldehyde resin or epoxy resin 0.0-5.0 Stabilizer 0.0-1.0Aromatic hydrocarbons 00-250 In accordance with a preferred form of theinstant invention, intercoat compositions are selected from the range ofcompositions as set forth in the following table:

TABLE III Ingredients: Percent by weight Vinyl chloride acetatecopolymers 5.0-10.0 Acrylic polymers 6.5-11.0

Alkyd-acrylic copolymers 2.3-5.7 Ethylacetate 23.0-36.0Methylisobutylketone 25.0-38.0 Cyclohexanone 1.0-3.9

Modified formaldehyde resin or epoxy rsein 1.5-4.2 Stabilizer 0.35-0.75

Aromatic hydrocarbons 12.0-23.5

Other ketones can be substituted for those listed and, with respect toTable I, it will be understood that the resins, stabilizers and aromatichydrocarbons can be utilized therein in essentially the proportions setforth in Tables II and III.

It will be noted that the vinyl chloride acetate copolymer is includedin lesser amounts when the acrylic and alkyd-acrylic is included. Thus,these latter ingredients act as substitutes for a portion of the formerwhereby a maximum of about 23 percent by Weight of these ingredients areincluded in the film as applied. It is again emphasized, however, thatthe amount of diluent or solvent can be varied for applicationconvenience. Based on the ranges of Table II, these ingredients arepresent, in the final coating, between a maximum of about 7 parts and aminimum of about 0.6 part of acrylic or alkydacrylic to one part of thevinyl chloride acetate copolymer.

The following disclosure sets forth typical compounds falling into theclasses of compounds discussed above and suitable for use in accordancewith the features of this invention. It will be understood that theparticular compounds referred to herein are only considered to beillustrative of the great number of compounds which also fall within thescope of the instant invention.

In the case of acrylic polymers, Acryloid B72, B66, A11, and B44supplied by Rohm & Haas and Lucite 2013, 2044, 6014 and 6016 supplied bydu Pont are preferred. The group comprisesmethyl-methacrylate/ethyl-acrylate copolymer, methylmethacrylatecopolymers, N-butyl methacrylate, and butyl-methacrylate copolymer. Itwill be appreciated from the above examples that the instant inventioncontemplates the use of any acrylic polymer comprising a methyl-,ethyl-, butylor isobutyl-variation of methacrylate and acrylate.Copolymers are preferred; however, certain homopolymers are perfectlysuitable for the practice of this invention.

Of the alkyds, Duraplex ND76, ND77B, ND78 and C45 supplied by Rohm &Haas are considered particularly suitable. The alkyd-acrylic copolymersare preferably selected from the group comprising Amerlac 292X suppliedby Rohm & Haas, Lustrasol 13-137 supplied by Reichold and Chempol13-1410 supplied by Freeman.

Modified formaldehyde resins may comprise ureaformaldehyde such asF-240, melamine formaldehyde such as MM55 and triazine formaldehyde suchas MX61, all supplied by Rohm 8: Haas.

Suitable epoxy resins comprise Epi-Rez 510 supplied by Jones-Dabney,Araldite 6005 supplied by Ciba or Epon 828 supplied by Shell Chemical.

A wide variety of stabilizers are available including Drapex 6.8(epoxidized soybean oil), Mark 275, 180, 445 and 446 (benzophenon typelight stabilizer) supplied by Argus Chemical Corporation, Paraplex G60and G62 supplied by Rohm & Haas, Flomax 25, CS-137, Provinite andClarite A and B supplied by National Lead.

The compositions of the products referred to above by trademarkdesignations are as follows:

2013A methyl/n-butyl methacrylate copolymer having a typical inherentviscosity of 0.20 as measured in a solution of 0.25 g. polymer in 50 ml.of chloroform measured at 20 C. using a No. 50 Cannon-Fenske Viscometer.All inherent viscosities on these resins are measured in a similarmanner. Ell/.acite 2013 has a specific gravity of 1.16.

2044-An n-butyl methacrylate polymer having a typical inherent viscosityof 0.53. It is considered to be a high molecular weight resin and has aspecific gravity of 1.07.

6014-A methyl methacrylate copolymer having a typical inherent viscosityof 0.45 and is considered to be a medium molecular weight resin. Thisresin is supplied as a solution, 40% supplied in a mixture of 80 partstoluene to 20 parts isopropanol. It has a specific gravity of 1.16 andan acid number of 12 to 15.

6016A methyl/n-butyl methacrylate copolymer having a typical inherentviscosity of 0.26. This is considered a low molecular weight resin. Itis furnished as a 40% solution in toluene. It has a specific gravity of1.12 and an acid number of 2.5 to 4.0.

All of these Elvacite resins are described in a booklet by du Pontentitled Properties of Elvacite Acrylic Resins, copyrighted 1966 andnumbered A45610 (M, 1/66).

Acryloid B72Is supplied as a 40% solid resin in toluene, having aspecific gravity of 0.96; a viscosity in centipoises at 30 C. of 480640.

Acryloid B66Is supplied as a 40% solid resin in toluene, having aspecific gravity of 0.97; a viscosity in centipoises at 30 C. 250-335.

Acryloid B44-Is supplied as a 40% resin solution in toluene, having aspecific gravity of 0.98; a viscosity in centipoises at 30 C. of6001100.

The information on the Acryloid resins was obtained from a bookletentitled AcryloidAcrylic Ester Resins for Coatings by Rohm & Haas,copyrighted 1958Numbered C-46-5 8 (Revised February 1962).

Duraplex D76Is an alkyl resin containing phthalic anhydride and based oncoconut oil. Material on a solids basis has an acid number of 48.Solution in xylol containing 60% solids has a density of 8.4 lbs./gallon.

Duraplex ND77B-Is an alkyl resin containing 47% phthalic anhydride on asolids basis and 33% coconut oil. It has an acid number on a solidsbasis of 410. Solution in xylol containing 60% solidsdensity 8.6lbs/gallon.

Duraplex ND78-Is an alkyd resin containing 43% phthalic anhydride and33% coconut oil, having an acid number based on solids of 610. Solutionis xylol of 60% solidsdensity of 8.5 lbs/gallon.

Duraplex C-45 Is furnished in two grades: HV nd LV.

HV-An alkyl resin containing 33% phthalic anhydride on a solids basisand 53% linseed oil, having an acid number of 5-15 on a solids basis.Solution in mineral thinner containing 60% solids, has a density of 7.9lb s./ gallon.

LVAn alkyd resin containing 30% phthalic anhydride on a solids basis and60% linseed oil, having an acid number of 9-18 on a solids basis and adensity of 9.0 lbs./gallon.

This information was obtained from a booklet by Rohm & Haas entitledDuraplex and AmberlacAlkyd Type Resins, 1958, No. C-48-58, April 1961edition.

Amberlac 292XAn alkyd-acrylic resin based on castor oil having an acidnumber on a solids basis of 13 maximum, as a solution having 48% solidsin xylol and having a density of 7.9 lbs./ gallon.

The reference is the same booklet as cited for the alkyd resins above.

Lustrasol 13-137An alkyd modified acrylic resin furnished as a solutionof 59 to 61% solids in Solvesso 150 solvent, having an acid number of 7maximum, and a specific gravity of 1.027 to 1.037.

Chempol 13-1410-An acrylic alkyl copolymer based on safilower oil,containing 14% phthalic anhydride and exhibiting an acid number of 3 to7. Supplied as a 50% solids solution in xylol. This is sold by theFreeman Chemical Company.

Uformite F-240A urea formaldehyde resin containing 60% solids, furnishedas a xylol-butanol mixture (1:1 /2) having an acid number on a solidsbasis of 3 to 8, a specific gravity of 1.02.

Uformite MM-55A melamine formaldehyde resin containing approximately 50%solids in a xylol-butanol mixture of 1:4, having an acid number on asolids basis of 0 to 2, a specific gravity of 0.97.

Uformite MX-6 1A triazine formaldehyde resin containing approximately60% solids in a xylol-butanol 1:1 mixture. It has an acid number on asolids basis of 0 to 1, a specific gravity of 1.04.

The information on these modified formaldehyde resins was obtained froma booklet by Rohm & Haas entitled UformiteUrea, Melamine and OtherTriazine Formaldehyde Resins for Finishes, No. C-5058, December 195 8,Revised November 1964.

Epi-Rez 510-A bis phenol A based epoxy resin having a weight epoxy of180 to 200, a specific gravity of 1.16, a viscosity of 10,000 to 16,000centipoises at 25 C.

This information was obtained from a technicalbooklet by Johnes-DabneyCo., dated May 1, 1962.

Araldite 6005-A low viscosity, liquid epoxy resin, having a viscosity incentipoises at 25 C. of 7000 to 10,000, an epoxy value equivalence perg. of 0.53 to 0.55, weight per gallon of 9.6 to 9.8.

This information was found in a Ciba technical bulletin on epoxy resins,No. 20820/ 7.

Epon 828A light colored, epichlorohydrin/bisphenol A-type, low molecularweight epoxy resin, having a viscosity at 25 C. of 100 to poises and anepoxy equivalent of 185 to 192. It has a density of 1.168 at 20 C., arefractive index at 25 C. of 1.570 to 1.575 and an average molecularweight of approximately 380. This material is made by the Shell ChemicalCompany and is described in a Shell Chemical Company Data SheetSC160-146R, July 1962.

Drapex 6.8Is epoxidized soybean oil, having a specific gravity of 0.990,a refractive index of 1.469, a freezing point of 0 C., an acid number of0.9 and a percentage of oxirane oxygen of 6.6.

This information was obtained from an Argus Technical Bulletin, No. 3,on Drapex Plasticizer, dated September 1961.

Mark 27An organotin stabilizer having a specific gravity at 25 C. of1.145, a refractive index at 25 C. of 1.484.

Mark 445 and 446 were similarlyboth identified in an undesignatedmimeographed sheet furnished by Argus.

Flomax 25.A liquid barium-cadium organic complex having a specificgravity at 25 C. of 1.03, a refractive index at 25 C. of 1.48. 1

Information found in a Dutch Boy Flomax 25 Bulletin by National LeadCompany.

Mark 180-A liquid barium-cadium stabilizer having a specific gravity at25 C. of 1.022 and a refractive index at 25 of 1.490.

CS-137A barium-sodium organic complex having a specific gravity of 1:54and a refractive index of 1.48. Supplied as a 70% solids content pastein dioctyl phthalate.

Information from Dutch Boy Bulletin CS-137.

ProviniteA barium-cadmium organic complex. 'Furnished in two forms:

Provinite AA powder having a specific gravity of 1.31

and a refractive index of 1.53.

Provinite B-,-A liquid having a specific gravity of 0.992 and arefractive index of 1.513.

Both of these compounds are furnished by National Lead and areidentified in a technical bulletin entitled Dutch Boy Provinite.

Paraplex G 60-A high molecular weight oil epoxide plasticizerstabilizermolecular weight 1,000; specific gravity 0.990; lbs/gallon8.3; viscosity at 25 C., 2.5 poises; refractive index at 25 C. 1.472;acid number 0.3.

Information from bookPlasticizer Perplex and Monoplex Rohn & Haas 1960.

Paraplex G 62Oil epoxide plasticizer stabilizermolecular weight 1,000;viscosity 3,5 at 25 C.; refractive index 1.471; acid number 0.4;specific gravity 0.993.

The following comprise specific examples of intercoat compositionsfalling within the preferred aspects of the instant invention:

Where the composition of Example II is employed, vinyl and polyestermaterials can be coated with a film of the composition, and thematerials can be immediately passed to a baking device. The bakingoperation preferably comprises heating of the materials to a temperatureabove 40 C. but preferably not exceeding 90 C. to drive out volatiletraces thereby improving adhesion and resistance to aging. When anoperation of this nature is carried out for from 30 seconds to minutes,the intercoat composition will be completely dry to the extent thatcontinuous sheets can 'be formed into rolls while individual lengths ofthe material can be stacked on top of each other without danger ofsticking of the coating to the back sides of adjacent sheets. Thecoatings are characterized by ideal adhesion and they have been found tobe completely compatible with respect to printing inks of virtually anycomposition. Accordingly, the compositions of this invention achieve theresults accomplished in the aforementioned copending applications whilealso providing improved production etficiency.

It will also be appreciated that the coatings can be air dried asindicated in Ser. No. 395,331. The removal of the solvent is, however,substantially slower where air drying is concerned and, therefore, airdrying is not nearly as efficient from the standpoint of commercialoperations.

As previously noted, the intercoat compositions are also characterizedby a desirable degree of plasticity whereby handling case can berealized. High chemical resistance is achieved particularly due to thepresence of the formaldehyde resins or epoxy resins andalkyd-acryliccopolymers. These alkyd-acrylic-copolymers are alsoeffective to increase the stability of the intercoat composition. Anadditional advantage of the instant invention resides in the fact thataromatic hydrocarbons can be employed as diluents, and since suchmaterials are relatively cheap,

the compositions of the invention are not unduly expensive.

With particular reference to vinyl films, it is to be noted that suchfilms can be readily given the appearance of a colored film therebyovercoming difiiculties encountered in this respect when employing priorart techniques. In one suitable procedure for providing such films,coatings comprising alkyd or nitrocellulose based vehicles and includingsuitable pigments can be readily applied over vinyl surfaces having thedescribed intercoat composition applied thereto. Naturally, thisarrangement can also be employed with other surfaces includingpolyester.

It is also important to note that coatings of the type described hereincan have pigments or dyes added directly thereto whereby the applicationof the intercoat will impart a colored appearance to a vinyl orpolyester surface. Finally, standard printing methods could be employedfor any ink of any color on the intercoat surfaces.

Where an intercoat of this invention is first applied to a vinyl orpolyester substrate, printing inks and lacquers can be readily appliedand provide extremely satisfactory quality. Compositions applied includeprinting inks and coatings based on acrylic, and methacrylic esterresins, alkyd resins, nitrocellulose, vinyl butyral resin,urea-formaldehyde resins, melamine resins, oleoresinous vehicles,shellac and varnishes.

Where reference is made in the foregoing specification and in theappended claims to copolymers of vinyl chloride and vinyl acetate, itwill be appreciate that the socalled modified copolymers are includedwithin the scope of the invention. Examples of such modified materials,which may comprise VAGH, VAGD, VMCH and VMCC, are found in Lox et al.Patent No. 3,137,666.

That which is claimed is:

1. In a method for applying materials consisting of inks and coatingsselected from the group consisting of alkyd and nitro-cellulose basedmaterials onto surfaces of the group consisting of vinyl and polyestersurfaces, the improvement comprising forming a film over one of saidsurfaces, said film consisting essentially of from 10 to 20 percent byweight vinyl chloride-acetate copolymer, from 7.5 to 20 percent byweight of at least one member selected from the group consisting ofacrylic polymers containing 1 to 4 carbon atoms and alkydacrylic-copolymers, and the balance a solvent selected from the groupconsisting of saturated and unsaturated ketones, nitro compounds,aromatic hydrocarbons, esters, chlorinated hydrocarbons and combinationsthereof, thereafter drying said film to remove substantially all of saidsolvent, and applying one of said materials over said film.

2. A method in accordance with claim 1 wherein said surfaces are of thegroup consisting of polyvinyl chloride and polyvinyl acetate.

3. A method in accordance with claim 1 wherein said film is force driedby the application of heat.

4. A method in accordance with claim 1 wherein said film is air dried.

5. A method in accordance with claim 1 wherein said film contains up toabout 1 percent by weight polyvinyl chloride.

6. A method in accordance with claim 1 wherein said film includes from0.0 to 5.0 percent by weight of a member selected from the groupconsisting of modified formaldehyde resins and epoxy resins, from 0 to1.0 percent by weight stabilizers, and from 0 to 25.0 percent by weightaromatic hydrocarbons.

7. A method in accordance with claim 1 wherein said film includes amaterial selected from the group consisting of pigments and dyes wherebysaid film provides a colored surface on said vinyl and polyester.

8. A method in accordance with claim 1 wherein said solvent includes atleast one of the members selected from the group consisting ofisophorone and cyclohexanone comprising from one to five percent byweight of the film.

9. A method in accordance with claim 8 wherein the balance of saidsolvent consists of at least one member selected from the groupconsisting of methylethylketone, methylisobutylketone and ethylacetate,said group comprising from 45 to 75 percent by weight of said film.

10. An article of manufacture formed from a material selected from thegroup consisting of vinyl and polyester materials, said materialcomprising the base portion of said article, an intercoat compositionapplied over said base portion, said intercoat composition consistingessentially of vinyl chloride-acetate copolymer and at least one memberselected from the group consisting of acrylic polymers containing 1-4carbon atoms andalkyd-acrylic copolymers, and-an outer coating in theform of printed material applied over at least a portion of the surfaceof said intercoat composition, said outer coating comprising acomposition selected from the group consisting of alkyd and nitrocellulose based materials, said acrylic and alkyd-acrylic being presentin said intercoat composition in a ratio between a maximum of about 7parts and a minimum of about 0.6 parts to one part of the vinylchloride-acetate copolymer.

11. An article in accordance with claim 10 wherein References CitedUNITED STATES PATENTS 2,427,513 9/1947 Spessard 260132.8 X 2,770,56611/1956 Ritter l1773 X 2,872,423 2/1959 Goldstein 1l 7 l3,8.8 X3,136,657 6/1964 Dixler et al 1l7l38.8 3,231,393 1/1966 Downing 1-l7l61X 3,305,602 2/1967 Bromstead 260-328 X 3,323,943 6/1967 Bromstead 117161X ALFRED L. LEAVITT, Primary Examiner 20 A. GRIMALDI, Assistant ExaminerUS. 01. X.R. 117-45, 72, 138.8, 161; 260 -32.8, 33.8

